Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof

ABSTRACT

Described is the schiff base reaction product of methyl anthranilate having the structure: ##STR1## with ethyl vanillin having the structure: ##STR2## a compound having the structure: ##STR3## and uses thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles including perfumed polymers and colognes. The schiff base having the structure: ##STR4## also has unexpected, unobvious and advantageous utilities for its deodorancy properties in addition to having valuable properties as a fragrance material.

This is a divisional of application Ser. No. 134,978, filed 12/18/87 nowabandoned.

BACKGROUND OF THE INVENTION

Our invention relates to the novel reaction product which is the schiffbase of ethyl vanillin and methyl anthranilate, the compound having thestructure: ##STR5## and the organoleptic use thereof in augmenting orenhancing the aroma of perfume compositions, colognes and perfumedarticles and in enhancing or augmenting the effect of deodorancy; as amaskant for malodors emanating from the axillary regions of mammalianspecies.

Inexpensive chemical compositions of matter which can provide sweet,vanilla bean-like and sassafras aroma profiles with sweet topnotes andwhich are highly substantive and long-lasting are highly desirable inthe art of perfumery. Many of the natural materials which provide suchfragrances and contribute desired nuances to perfumery compositions aswell as perfumed articles including solid or liquid anionic, cationic,nonionic or zwitterionic detergents, fabric softener compositions andfabric softener articles are high in cost, vary in quality from onebatch to another and/or are generally subject to the usual variations ofnatural products.

Still more desirable are materials which can both provide usefulfragrance effects including high substantivity and a long-lastingfragrance and also provide a deodorancy effect whereby malodors can bemasked by means of the use of the compound in, for example, the axillaryregions of mammalian species including human beings.

Reaction products of carbonyl-containing compounds and amine-containingcompounds are well known in the art of flavoring and in the art of ofperfumery. Thus, U.S. Pat. No. 4,618,501 issued on Oct. 21, 1986discloses the flavoring of foodstuffs with alpha,beta-keto-amines andstates that an alpha,beta-keto-amine having a nutty corn, cereal aromamay be used for flavoring compositions for foods having the structure:##STR6## wherein R₁, R₂ and R₃ are selected from the group consisting ofa saturated or unsaturated alkyl straight or branched chain hydrocarbonshaving from 1-3 carbon atoms.

U.S. Pat. No. 3,625,710 issued on Dec. 7, 1971 discloses the use ofaldimines as chocolate-like flavors which aldimines are resulting fromthe reaction product of amines and aldehydes, for example,N-isobutylidenefurfurylamine, N-isopentylidenefurfurylamine,N-isopentylideneisopentylamine.

Schiff bases are also well known in the art of perfumery. Thus, forexample, Chemical Abstracts Volume 103, 1985, No. 123134z (Abstract ofJapan Kokai No. 60/78951 discloses the use in perfumery of compoundshaving the structure: ##STR7##

Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume II,published by the Author in 1969 discloses the organoleptic properties ofthe schiff base of methyl anthranilate and vanillin having thestructure: ##STR8## thusly: ##STR9## Viscous, dark-yellowish liquid,occasionally with an orange-reddish tint, or an olive-green color.

Insoluble in water, soluble in alcohol and oils.

Intensely sweet, balsamic-floral odor of very good tenacity. The odorvaries considerably from one sample (supplier) to another, a fact whichis often observed in "Schiff's bases". Generally, a mild surplus of thealdehyde component is preferable, except in cases of very pungentaldehydes such as Cuminaldehyde, Cinnamic aldehyde, Methylcinnamicaldehyde, etc.

The title material has very little use in perfumes, and is simplymissing from most perfume laboratories. It may be considered as acuriosity, more than a practical perfume material, but it is brieflymentioned in this work because it may often "occur" in a perfume, sincethe use of Vanillin and Methylanthranilate in the same composition isnot a very rare or unusual case. The addition of Vanillin directly intoMethylanthranilate may often cause a strong coloring, brown or orange,of the mixture, and it is recommended not to add these materials insequence, one next to the other.

Among scores of suggested "Schiff's bases", only very few have becomestandard perfume items, and the title material is not one of them. Butit is classified as "interesting", by some perfumers.

Prod.: by condensation of Vanillin with Methylanthranilate in molecularproportions, preferably in a suitable diluent to prevent violentdarkening, and to render the final product more pourable, handy for use.

Arctander also discloses the organoleptic properties of vanillin-ethylcarbonate-phenetidine, thusly: ##STR10## Yellowish needle-like crystals.M.P. 88° C.

Very slightly soluble in water, moderately soluble in alcohol, solublein hot alcohol and oils.

The title material is briefly mentioned because it behaves in a ratherpeculiar manner. Although it has an unquestionable odor ofVanillin-type, rather soft, but quite pleasant and not exactly weak, itsaqueous solution or the dry material itself has hardly any taste at all.

This peculiarity has not been explained in literature, but it could wellbe that the material (molecule), part of which is an aromaticaminoether, has mildly anaesthetic effect upon the human mucousmembranes. Many members of this chemical series have anaesthetic effect.

The material was developed many decades ago for pharmaceutical purposes,but was also introduced to the perfume and flavor industry at that time.It has no longer importance to perfumes or flavors, but it is still usedin pharmacy.

The compound of our invention having the structure: ##STR11## hasunexpected, unobvious and advantageous organoleptic properties includingdeodorancy properties as opposed to the compounds of the prior artincluding the compound having the structure: ##STR12##

The book "Flavor & Fragrance Materials-1987" published by AlluredPublishing Corporation, P. O. Box 318, Wheaton, Ill. 60189-0318discloses on page 154 the commercial availability of the followingschiff bases:

Methyl anthranilate and amyl cinnamic aldehyde;

Methyl anthranilate and hydroxy citronellal;

Methyl anthranilate and lilial;

Methyl anthranilate and anisic aldehyde;

Methyl anthranilate and decanal;

Methyl anthranilate and lyral;

Methyl anthranilate and iso-nonylaldehyde;

Methyl anthranilate and phenylacetaldehyde.

Schiff bases are also known to be useful as intermediate in producingother fragrance materials. Thus, U.S. Pat. No. 3,898,283 issued on Aug.5, 1975 discloses novel schiff base intermediates used in producing 4 or5 phenylpentenals having the structure: ##STR13## wherein X is from thegroup consisting of: ##STR14## and wherein R_(a) is hydrogen or methyl.

Nothing in the prior art however discloses the novel reaction productsor reaction product mixtures of our invention having unobvious,unexpected and advantageous organoleptic properties.

Indeed, nothing in the prior art is indicative of the novel schiff basereaction products of our invention having deodorizing properties thatis, having a deodorant value of 0.50 up to 3.5 as measured by thedeodorant value test described in U.S. Pat. No. 4,304,679 incorporatedby reference herein or having a Lipoxidase-inhibiting capacity of atleast 50% and a Malodour reduction value of from 0.25 up to 3 asmeasured by the Malodour reduction value test disclosed in U.S. Pat. No.4,663,068 incorporated by reference herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the reaction product of ethyl vanillin and methylanthranilate, having the structure: ##STR15##

FIG. 2 is the mass spectrum for the compound having the structure:##STR16## produced according to Example I.

FIG. 3 is a cut-away side elevation schematic diagram of a screwextruder during the compounding of a resin with the schiff base of ourinvention having the structure: ##STR17## while simultaneously addingfoaming agent into the hollow portion of the barrel of the extruder andincorporates the pelletizing apparatus used in pelletizing the extrudedfoamed tow produced as a result of the extrusion operation.

FIG. 4 represents a cut-away side elevation view of apparatus used informing perfumed polymers which contain imbedded therein the schiff baseof our invention having the structure: ##STR18##

FIG. 5 is a front view of the apparatus of FIG. 4 looking in thedirection of the arrows.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the compound having the structure: ##STR19## (Conditions: 50m×0.32 mm OV-1fused silica column, programmed at 60°-220° C. at 4° C.per minute). The peak indicated by reference numeral 101 is the peak forthe methyl anthranilate reactant having the structure: ##STR20## thepeak indicated by reference numeral 102 is the peak for the ethylvanillin reactant having the structure: ##STR21## The peak indicated byreference numerals 103 is the peak for the reaction solvent, the diethylphthalate solvent. The peak indicated by reference numeral 104 is thepeak for the schiff base reaction product having the structure:##STR22##

Referring to FIG. 3, FIG. 3 is a schematic cut-away elevation diagram ofthe extrusion and pelletizing apparatus useful in carrying out a processfor incorporation of the schiff base of our invention having thestructure: ##STR23## into polymers during the operation of saidapparatus. Motor 15 drives the extruder screws located at 23A in barrel16, the extruder being operated at temperatures in the range of about150° up to about 250° C. At the beginning of the barrel, resin at source12 together with additives, e.g., opacifiers, processing aids, colors,pearlescent agents and densifiers at location 13 is added via additionfunnel 14 into the extruder. Simultaneously (when the operation reaches"steady state") the schiff base of our invention having the structure:##STR24## is added to the extruder at one, two or more of barrelsegments 3-8 of the extruder (which may be a twin screw or single screwextruder) at locations 18a, 18b, 18c and 18d by means of gear pump 23from source 17. From source 19 into barrel segments 5-10, the gaseous orliquid blowing agents, e.g., nitrogen, carbon dioxide and the like areadded simultaneously with the addition of the schiff base of ourinvention having the structure: ##STR25## The feed rate range of theresin is about 80-300 pounds per hour. The feed rate range of the schiffbase taken alone or further together with other perfumant(s) is between1 and 45% of the feed rate range of the resin. The blowing agent raterange is such that the pressure of the gas or the pressure over theliquid being fed into the extruder is between about 50 and 200 psig. Ifdesired, the extruded ribbon or cylinder may be passed through waterbath 20 and pelletizer 21 into collection apparatus 21a.

Referring to FIGS. 4 and 5, there is provided a process for formingscented polymer pellets (wherein the polymer may be thermoplasticpolymers such as low density polyethylene or polypropylene or copolymersof ethylene and vinyl acetate or mixtures of polymers and copolymerssuch as copolymers of ethylene and vinyl acetate and polyethylene) suchas pellets useful in the formation of plastic particles useful infabricating certain articles which may be perfumed. This processcomprises heating the polymer or mixture of polymers to the meltingpoint of said polymer or mixture of polymers, e.g., 250° C. in the caseof low density polyethylene. The lower most portion of the container ismaintained at a slightly lower temperature and the material in thecontainer is taken off at such location for delivery through theconduit. Thus, referring to FIGS. 4 and 5, in particular, the apparatusused in producing such elements comprises a device for forming thepolymer containing perfume, e.g., polyethylene or polyethylene-polyvinylacetate or mixtures of same or polypropylene, which comprises a vat orcontainer 212 into which the polymer taken alone or in admixture withother polymers or copolymers and the perfuming substance which is atleast one of the schiff base having the structure: ##STR26## and othercompatible perfumes is placed. The container is closed by means of anair-tight lid 228 and clamped to the container by bolts 265. A stirrer273 traverses the lid or cover 228 in an air-tight manner and isrotatable in a suitable manner. A surrounding cylinder 212A havingheating coils which are supplied with electric current through cable 214from a rheostat or control 216 is operated to maintain the temperatureinside the container 212 such that the polymer in the container will bemaintained in the molten or liquid state. It has been found advantageousto employ polymers at such a temperature that the viscosity will be inthe range of 90-100 sayboldt seconds. The heater 218 is operated tomaintain the upper portion of the container 212 within a temperaturerange of, for example, 220°-270° C. in the case of low densitypolyethylene. The bottom portion of the container 212 is heated by meansof heating coils 212A regulated through the control 220 connectedthereto through a connecting wire 222 to maintain the lower portion ofthe container 212 within a temperature range of 20°- 270° C.

Thus, the polymer or mixture of polymers added to the container 212 isheated from 10-12 hours, whereafter the perfume composition or perfumematerial which contains a schiff base of our invention having thestructure: ##STR27## is quickly added to the melt. Generally, about10-45 percent by weight of the resulting mixture of the perfumerysubstance is added to the polymer.

After the perfume material containing the schiff base of our inventionis added to the container 212 the mixture is stirred for a few minutes,for example, 5-15 minutes and maintained within the temperature rangesindicated previously by the heating coil 212A. The controls 216 and 220are connected through cables 224 and 226 to a suitable supply ofelectric current for supplying the power for heating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer in intimate admixture with the schiffbase of our invention having the structure: ##STR28## or mixture ofperfume substances and the schiff base of our invention, willcontinuously drop through the orifices 234 downwardly from the conduit232. During this time, the temperature of the polymer intimately admixedwith the perfumery substance in the container 212 is accuratelycontrolled so that a temperature in the range of from about 240°-250°C., for example, (in the case of low density polyethylene) will exist inthe conduit 232. The regulation of the temperature through the controls216 and 220 is essential in order to insure temperature balance toprovide for the continuous dropping or dripping of molten polymerintimately admixed with the perfume substance which at least containsthe schiff base of our invention having the structure: ##STR29## throughthe orifices 234 at a rate which will insure the formation of droplets236 which will fall downwardly onto a moving conveyor belt 238 caused torun between conveyor wheels 240 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238, they form pellets 244which harden almost instantaneously and fall off advantageously filledwith water or some other suitable cooling liquid to insure the rapidcooling of each of the pellets 244. The pellets 244 are then collectedfrom the container 250 and utilized for the formation of otherfunctional products, e.g., garbage bags and the like.

THE INVENTION

Our invention provides the schiff base having the structure: ##STR30##produced by means of reaction of ethyl vanillin having the structure:##STR31## with methyl anthranilate having the structure: ##STR32##according to the reaction: ##STR33##

More specifically, the schiff base of our invention having thestructure: ##STR34## produced according to the process of our inventionis capable of augmenting or enhancing or modifying the aromacharacteristics of perfume compositions, colognes and perfumed articles(including soaps, anionic, cationic, nonionic or zwitterionicdetergents, fabric softener compositions, optical brightenercompositions and drier-added fabric softener articles) and perfumedpolymers by imparting thereto an intense and surprisingly tenaceous andsubstantive sweet, vanilla bean-like and sassafras aroma profile withsweet topnotes thus fulfilling a need in the field of perfumery anddetergents and cosmetic manufacture.

The schiff base of our invention having the structure: ##STR35## is alsocapable of deodorizing detergent powders suitable for use in the washingof fabrics as well as detergent powders as well as hand soaps. Suchdetergent powders include bleaching compositions, for example, bleachingcompositions comprising a peroxy bleach compound. The schiff base of ourinvention having the structure: ##STR36## has a deodorancy value asmeasured by having a Lipoxidase-inhibiting capacity of at least 50% anda Raoult Variance ratio of at least 1.1 and a malodour reduction valueof between about 0.25 up to 3.0 as measured by the malodour reductionvalue test disclosed in U.S. Pat. No. 4,663,068 the specification forwhich is incorporated by reference herein; and in addition, a deodorantvalue of from 0.50 up to 3.5 as measured by the deodorant value test asdisclosed in U.S. Pat. No. 4,304,679 the specification for which isincorporated by reference herein.

The reaction to form the schiff base having the structure: ##STR37##between ethyl vanillin having the structure: ##STR38## and methylanthranilate having the structure: ##STR39## has the followingparameters: (i) the temperature of the reaction is in the range of fromabout 90° C. up to about 150° C.;

(ii) the pressure over the reaction mass may vary from about 3 mm/Hg.(vacuum) up to about 1 atmosphere with a preferable pressure of betweenabout 5 and about 100 mm/Hg. pressure;

(iii) the time of reaction may vary from about 3 up to about 15 hourswith a preferred time of reaction of between about 6 and about 12 hours;

(iv) the mole ratio of ethyl vanillin having the structure: ##STR40## tomethyl anthranilate having the structure: ##STR41## may vary from about1:1 up to about 1.25:1 of total ethyl vanillin:methyl anthranilate witha preferred mole ratio of between about 1:1 and about 1.1:1 ethylvanillin:methyl anthranilate.

At the end of the reaction, the reaction mass may be separated and thereaction product purified as by fractional distillation of the schiffbase having the structure: ##STR42## From a practical standpoint when areaction mixture is created which gives rise to preferred perfumeryproperties, subsequent fractional distillation to the point of yieldingan odor acceptable product is what is desired.

The schiff base having the structure: ##STR43## prepared in accordancewith the process of our invention and one or more auxiliary perfumeingredients including, for example, alcohols, aldehydes, ketones,terpinic hydrocarbons, nitriles, esters, lactones, natural essentialoils and synthetic essential oils may be admixed so that the combinedodors of the individual components produce a pleasant and desiredfragrance, particularly, and preferably, in floral and lavenderfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling, freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the schiffbase derivative having the structure: ##STR44## prepared in accordancewith the process of our invention, can be used to alter, modify orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of schiff base derivative having the structure: ##STR45##prepared in accordance with the process of our invention which will beeffective in perfume compositions as well as in perfumed articles (e.g.,anionic, nonionic, cationic and zwitterionic solid or liquid detergents,soaps, fabric softener compositions, drier-added fabric softenerarticles, optical brightener compositions, perfumed polymers and textilesizing agents) and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% ofschiff base derivative having the structure: ##STR46## prepared inaccordance with the process of our invention and less than 50% of saidschiff base derivative or even less (e.g., 0.005%) can be used to impartsweet vanilla bean-like and sassafras aroma profiles with sweet topnotesto solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, fabric softener compositions, fabric softener articles,optical brightener compositions, textile sizing compositions, perfumedpolymers or other products. The amount employed can range up to 100% ofthe fragrance components and will depend on considerations of cost,nature of the end product, the effect desired on the finished productand the particular fragrance sought.

The schiff base derivative having the structure: ##STR47## prepared inaccordance with the process of our invention is useful (taken alone ortogether with other ingredients in perfume compositions) as (an)olfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such ascreams, deodorants, hand lotions and sun screens; powders, such astalcs, dusting powders, face powders, and perfumed polymers and articlesof manufacture produced from said perfumed polymers. When used as (an)olfactory component(s) as little as 0.2% of schiff base derivativehaving the structure: ##STR48## prepared in accordance with the processof our invention will suffice to impart an intense and substantive sweetvanilla bean and sassafras aroma profile with sweet topnotes to floral,rose and fresh air formulations. Generally, no more than 6% of theschiff base of our invention having the structure: ##STR49## based onthe ultimate end product is required in the perfumed articlecomposition. Accordingly, the range of schiff base having the structure:##STR50## in the perfumed article is from about 0.2% by weight of theschiff base up to about 6% by weight of the schiff base based on theweight of the perfumed article.

In addition, the perfume composition of fragrance composition of ourinvention can contain a vehicle or carrier for the schiff base havingthe structure: ##STR51## prepared in accordance with the process of ourinvention. The vehicle can be a liquid, such as a non-toxic alcohol,e.g., ethyl alcohol, a non-toxic glycol, e.g., propylene glycol or thelike. The carrier can also be an absorbent solid, such as a gum (e.g.,gum arabic, guar gum or xanthan gum) or components for encapsulating thecomposition (such as gelatin) as by coacervation; or such asurea-formaldehyde polymers forming a capsule shell around a liquidperfume center).

Our invention also relates to the utilization of controlled releasetechnology for the controlled release of perfumes into gaseousenvironments from polymers such as mixtures of epsilon polycaprolactonepolymers and polyethylene which polyepsilon caprolactone polymers aredefined according to at least one of the structures: ##STR52## wherein"n" is from about 50 up to about 1,200 with the proviso that the average"n" in the system varies from about 150 up to about 700 according to themathematical statement:

    [700≧n≧150]

with the term "n" being the average number of repeating monomeric unitsfor the epsilon polycaprolactone polymer. The perfumed material'srelease rate from such polymer mixture is close to "zero order". As ageneral rule, the release rate in a polymeric matrix is proportional tot^(-1/2) until about 60% of the functional fluid is released from thepolymeric matrix. The release rate thereafter is related exponentiallyto time as a general rule according to the equation: ##EQU1## wherein k₁and k₂ are constants. According to Kydonieus, "Controlled ReleaseTechnologies: Methods, Theory, and Applications" (cited, supra, theamount of perfume composition released is proportional to time as longas the concentration of perfume material present, e.g., the schiff baseof our invention having the structure: ##STR53## is higher than thesolubility of the agent in the matrix. Thus, such dispersed systems aresimilar to the dissolved systems except that instead of a decreasedrelease rate after 60% of the perfume material has been emitted, therelationship holds almost over the complete release curve. Kydonieusfurther states, that if one assumes that the release of functional fluidby diffusion is negligible in monolithic erodible systems, the speed oferosion will control the release rate and release by erosion by asurface-area-dependent phenomenon, the release constant (zero order) aslong as the surface area does not change during the erosion period. Thisis the case with the polymers containing the schiff base of ourinvention having the structure: ##STR54##

The polyepsilon caprolactone polymers useful in practicing our inventionare more specifically described in the brochure of the Union CarbideCorporation, 270 Park Avenue, New York, N.Y. 10017, entitled "NEWPOLYCAPROLACTONE TERMOPLASTIC POLYMERS PCL-300 AND PCL-700". Thesepolyepsilon caprolactone polymers are composed of a repeating sequenceof non-polar methylene groups and relatively polar ester groups. Theaverage number of repeating monomeric units varies between 150 and 700depending on the particular "PCL" number. Thus, regarding PCL-300 theaverage number of repeating monomeric units is about 300. RegardingPCL-700, the average number of repeating monomeric units is 700.

The polyepsilon caprolactone homopolymers which are ultimately taken inadmixture with such materials as polyethylene useful in the practice ofour invention may also be stabilized using stabilizers as defined inU.S. Pat. No. 4,360,682 issued on Nov. 23, 1982, the specification forwhich is incorporated herein by reference. The stabilizing materialswhich stabilize the polyepsilon caprolactone useful in conjunction withour invention against discoloration are dihydroxybenzenes such ashydroquinone or compounds having the formula: ##STR55## in which R₁ isalkyl of from 1 to 8 carbon atoms, and R₂ is hydrogen or alkyl of 1 to 8carbon atoms. It is preferable to have such stabilizer in thepolyepsilon caprolactone homopolymer in an amount of from about 100 to500 ppm. Such stabilizers do not interfere with the functional fluidsdissolved and/or adsorbed into the polymeric matrix.

The method of incorporating the schiff base of our invention or perfumecompositions containing same into the polymers may be according to thetechnique of U.S. Pat. No. 3,505,432 issued on April 7, 1970 (thespecification for which is incorporated by reference herein) or U.S.Pat. No. 4,247,498 issued on Jan. 27, 1981, the disclosure of which isincorporated by reference herein.

Thus, for example, a first amount of liquid polyethylene-polyepsiloncaprolactone polymer mixture (50:50) is mixed with the schiff base ofour invention. Drops are formed from the mixture and the drops aresolidified. The solidified drops are then melted, if desired, with asecond amount of unscented low density polyethylene, for example, orpolypropylene, for example. Usually, but not necessarily, the secondamount of polymer is larger than the first amount. The resulting mixturethus obtained is solidified subsequent to or prior to ultimate castinginto a utilitarian shape.

Thus, in accordance with one aspect of our invention the imparting ofscent is effected in two stages. In a first stage, a 50:50(weight:weight) polyepsilon caprolactone, e.g., PCL-700: polyethylene inmolten form is admixed with a high percentage of the schiff base of ourinvention having the structure: ##STR56## and the mixture is solidifiedin the form of pellets or beads. These pellets or beads thus contain ahigh percentage of schiff base (e.g., up to 45% by weight of the entiremixture) and may be used as "master pellets" which thereafter, in asecond stage, if desired, may be admixed and liquified with additionalpolymers such as additional polyethylene or mixtures of polyethylene andpolyepsilon caprolactone in an unscented state, or unscentedpolypropylene. In addition, additional polymers or copolymers may beused, for example, copolymers specified and described in United KingdomPatent Specification No. 1,589,201 published on May 7, 1981, thespecification for which is incorporated by reference herein.

In accordance with the present invention the schiff base of ourinvention is added to the polymer in a large closed container or drumwhich is maintained under controlled temperature conditions while thepolymer in a melted condition is mixed with the schiff base having thestructure: ##STR57## under agitation.

In order that the perfume be added uniformly to the polymer, thetemperature of the melt is constantly controlled during the process. Thepolymer-perfume mixture is then directed through an elongated conduit orpipe element having a plurality of orifices adjacent to the lower mostportion thereof. The polymer enriched by the schiff base of ourinvention is permitted to drip through the orifices onto a continuouslymoving, cooled conveyor upon which the polymer containing the schiffbase of our invention having the structure: ##STR58## solidifies intosmall size pellets with the perfume imprisoned therein. The apparatususeful in conjunction with this process advantageously includes aconveyor of a material which will not adhere to the polymer whichcontains the schiff base of our invention.

In order that the droplets form into uniform pellets or beads, theconveyor is continuously washed with a liquid such as water to maintainthe surface relatively cool. The pellets are delivered by the conveyorinto a container and packaged for shipment.

The following Example I serves to illustrate a process for preparing theschiff base of our invention having the structure: ##STR59## Theexamples following Example II are illustrative of the organolepticutilities of the schiff base of our invention. All parts and percentagesgiven herein are by weight unless otherwise specified.

EXAMPLE I Preparation of Schiff Base of Methyl Anthranilate and EthylVanillin REACTION ##STR60##

Into a 2 liter, 3 neck reaction flask equipped with stirrer,thermometer, glass "Y" adapter, 1 liter addition funnel, steamdistillation head with a 45/50 bottom male joint attached to thereaction flask, head thermometer, curved fraction cutter with a 50 mlreceiver, heating mantle controlled with a "Therm-O-Watch", dry icetrap, Bennert Manometer, vacuum bleed valve and vacuum pump is placed226.5 grams of methyl anthranilate having the structure: ##STR61## (1.5moles).

Separately, 224.1 grams (1.35 moles) of ethyl vanillin is dissolved indiethyl phthalate (225 grams) by heating thereby forming a solutionweighing approximately 500 grams.

The diethyl phthalate/ethyl vanillin solution is added to the reactionmass with stirring dropwise over a one hour period while heating thereaction mass to 50° C. at atmospheric pressure.

At the end of the addition time of the ethyl vanillin/diethyl phthalatesolution, the reaction mass is placed under 50 mm/Hg. vacuum and heatedto 125° C. for 3.5 hours.

After sampling for completion of reaction, the reaction is thencontinued for another four hours while heating at 130° C. and graduallyincreasing the vacuum to 30 mm/Hg. vacuum.

The resulting product (crude reaction mass) is then fractionallydistilled.

FIG. 1 is the GLC profile for the reaction product (Conditions: 50 m×0.32 mm OV-1 fused silica column programmed at 60°-220° C. at 4° C. perminute).

The peak indicated by reference numeral 101 is the peak for the methylanthranilate having the structure: ##STR62##

The peak indicated by reference numeral 102 is the peak for the ethylvanillin reactant having the structure: ##STR63##

The peak indicated by reference numeral 103 is the peak for the diethylphthalate reaction diluent.

The peak indicated by reference numeral 104 is the peak for the reactionproduct, the schiff base having the structure: ##STR64##

FIG. 2 is the mass spectrum after fractional distillation for the schiffbase having the structure: ##STR65##

The resulting product has an excellent sweet, vanilla bean-like andsassafras aroma profile with sweep topnotes.

EXAMPLE II Floral Perfume Compositions

The schiff base reaction product of Example I having the structure:##STR66## has a sweet, vanilla bean-like and sassafras aroma profilewith sweet topnotes and has great warmth and richness and blends wellwith many floral concepts.

The following formulation is prepared:

                  TABLE I    ______________________________________    Ingredients        Parts by Weight    ______________________________________    Citronellol        12.3    Geraniol           2.5    Amyl Cinnamic Aldehyde                       24.6    Galaxolide ○®○ 50 (Trademark                       9.8    for the Tricyclic Isochroman    of International Flavors &    Fragrances Inc.)    Vertenex High Cis (Cis-t-                       7.4    Butylcyclohexenyl Acetate;    Para Isomer)    Rose Oxide         0.7    Cinnamic Alcohol   19.6    Aldehyde C-11 (n-Undecylenic                       0.5    Aldehyde)    Aldehyde C-12 (n-Dodecyl                       0.5    Aldehyde in 10% solution    in diethyl phthalate)    Citronellal (10% solution                       0.5    in diethyl phthalate)    Phenyl Ethyl Acetate                       2.5    Ylang Oil          1.2    Indisan (Hydrogenated                       3.7    derivative of reaction    product of Camphene and    Resorcinol)    Musk Ketone        5.0    Oakmoss Resin      0.5    Liatrix Absolute (10% in                       2.5    diethyl phthalate    Vetiver Acetate    1.2    Diethyl Phthalate  5.0    The schiff base having                       5.0    the structure:     ##STR67##    prepared according    to Example I.    ______________________________________

The schiff base having the structure: ##STR68## prepared according toExample I imparts sweet, vanilla bean-like and sassafras undertones withsweet topnotes to this floral fragrance formulation. Accordingly, thefragrance formulation can be described from an organoleptic standpointas:

"floral, with sweet, vanilla bean-like and sassafras undertones andsweet topnotes".

EXAMPLE III Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II    ______________________________________    Substance          Aroma Description    ______________________________________     ##STR69##         A sweet, vanilla bean- like and sassafras aroma                       profile with sweet topnotes.    prepared according    to Example I.    Perfume composition                       A floral, with sweet,    of Example II.     vanilla bean-like and                       sassafras undertones and                       sweet topnotes.    ______________________________________

EXAMPLE IV Perfumed Liquid Detergents

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApril 6, 1976 incorporated by reference herein) with aroma nuances asset forth in Table II of Example III are prepared containing 0.10%,0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in TableII of Example III. They are prepared by adding and homogeneously mixingthe appropriate quantity of substance in Table II of Example III in theliquid detergent. The detergents all possess excellent aromas as setforth in Table II of Example III, the intensity increasing with greaterconcentrations of substance as set forth in Table II of Example III.

EXAMPLE V Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example III are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample III are imparted to the colognes and to the handkerchiefperfumes at all levels indicated.

EXAMPLE VI Preparation of Soap Compositions

One hundred grams of soap chips (per sample) (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram sample of substances as set forth in Table II of Example III untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquid are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example III.

EXAMPLE VII Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Patent No. 1,007,948 (incorporated herein byreference):

    ______________________________________    Ingredient          Percent by Weight    ______________________________________    NEODOL ® 45-11 (a C.sub.14 -C.sub.15                        12    alcohol ethoxylated with    11 moles of ethylene oxide)    Sodium carbonate    55    Sodium citrate      20    Sodium sulfate, water brighteners                        q.s.    ______________________________________

The detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example III. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample III.

EXAMPLE VIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),non-woven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.);

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table II of Example III.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example III, supra, consist of a substrate coating havinga weight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table II of Example III isadmixed in each case with the outer coating mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a dryer on operation thereof ineach case using said drier-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table II of Example III,supra.

EXAMPLE IX Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Sreet, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 Grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________    Ingredients        Weight Percent    ______________________________________    Dioctyl sebacate   0.05    Benzyl alcohol     0.10    Dow Corning 473 fluid                       0.10    (prepared by the Dow    Corning Corporation)    Tween 20 surfactant                       0.03    prepared by ICI America    Corporation)    One of the perfumery                       0.10    substances as set forth    in Table II of Example III,    supra.    ______________________________________

The perfume substances as set forth in Table II of Example III add aromacharacteristics as set forth in Table II of Example III which are ratherintense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE X Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company)(3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation)(1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

GAFQUAT® 755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "COMPOSITIONB".

The resulting "COMPOSITION A" & "COMPOSITION B" are then mixed in a50:50 weight ratio of A:B and cooled to 45° C. and 0.3 weight percent ofperfuming substance as set forth in Table II of Example III is added tothe mixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of theblending period, the resulting material has a pleasant fragrance asindicated in Table II of Example III.

EXAMPLE XI

Each of the fragrance materials of Table II of Example III, supra, areadded to a 50:50 weight:weight mixture of low densitypolyethylene:polyepsilon caprolactone PCL-700 forming pellets withscents as set forth in Table II of Example III, supra.

75 Pounds of a 50:50 mixture of PCL-700 polyepsilon caprolactone(manufactured by the Union Carbide Corporation of New York, New Yorkhaving a melting point of about 180°-190° F.):Low density polyethylene,are heated to about 250° F. in a container of the kind illustrated inFIGS. 20 and 21. 25 Pounds of each of the fragrance materials as setforth in Table II of Example III, is then quickly added to the liquifiedpolymer mixture, the lid 228 is put in place and the agitating means 273are actuated. The temperature is then raised to about 260° F. and themixing is continued for 5-15 minutes. The valve "V" is then opened toallow flow of the molten polymer enriched with perfume ingredient toexit through the orifices 234. The liquid falling through the orifices234 solidifies almost instantaneously upon impact with the moving cooledconveyor 238. Polymer beads or pellets 244 having pronounced scents asdescribed in Table II of Example III, supra, are thus formed. Analysisdemonstrates that the pellets contain about 25% of the perfume materialso that almost no losses in the scenting substance did occur. Thesepellets may be called "master pellets".

50 Pounds of each batch of the scent containing "master pellets" arethen added to one thousand pounds of unscented polypropylene and themass is heated to the liquid state. The liquid is molded into thinsheets of films. The thin sheets of films have pronounced aromas as setforth in Table II of Example III, supra. The sheets of films are cutinto strips of 0.25" in width ×3" in length and placed into room airfresheners.

On operation of the room air freshener, after four minutes, the room ineach case has an aesthetically pleasing aroma with no foul odor beingpresent, the aroma being described in Table II of Example III, supra.

EXAMPLE XI

A fabric washing deodorant detergent powder product is prepared byadmixing the following ingredients:

    ______________________________________    Ingredients          Parts by Weight    ______________________________________    Linear alkylbenzene sulfonate                         9.0    C.sub.13 -C.sub.15 straight chain                         4.0    alcohols (30:30:40 mixture of    C.sub.13, C.sub.14, and C.sub.15 straight    chain alcohol)    Sodium tripolyphosphate                         16.0    ZEAOLIGHT            8.0    Sodium silicate      4.0    Magnesium silicate   0.8    Ethylene diamine     0.6    N,N,N',N'-[tetra(methylene                         0.9    phosphonic acid)] sodium carboxy    methyl cellulose    Anti-foam            1.5    Sodium Perborate tetrahydrate                         14.0    N,N,N',N'-Tetraacetyl                         4.2    Glycoluril    The schiff base reaction product                         0.35    of ethyl vanillin and methyl    antranilate produced according    to Example I having the    structure:     ##STR70##    Water                45.0    Sodium sulfate       5.0    ______________________________________

The resulting fabric washing deodorant detergent powder on use givesrise to a very pleasant "fresh air" aroma without any aestheticallydispleasing aromas subsequent to washing of fabrics in the standardwashing machine cycle.

Deodorant detergent products have also been prepared according toExamples I-IX of U.S. Pat. No. 4,304,679 incorporated by referenceherein.

Thus, exemplified herein by reference are the following:

(a) a deodorant detergent product comprising:

(i) from 0.5 to 99.99% by weight of a non-soap detergent activecompound; and

(ii) from 0.01 to 10% by weight of a deodorant composition comprisingfrom 45 to 100% by weight of the schiff base of our invention having thestructure: ##STR71## said schiff base having a lipoxidase-inhibitingcapacity of at least 50% or a Raoult variance ratio of at least 1.1 asstated in said U.S. Pat. No. 4,304,679, with the schiff base compositionhaving the structure: ##STR72## having a deodorant value of from 0.5 to3.5 as measured by the deodorant value test as specifically set forth insaid U.S. Pat. No. 4,304,679 and exemplified therein.

Furthermore, the examples of U.S. Pat. No. 4,663,068 are alsoincorporated herein by reference.

Thus, exemplified herein are detergent powder products suitable for thewashing of fabrics comprising:

(i) from 5 to 40% by weight of a non-soap detergent active compoundcomprising an anionic detergent active compound;

(ii) from 1 to 90% of a non-soap detergency builder;

(iii) from 1 to 30% by weight a peroxy bleach compound together with anactivator therefor;

(iv) from 0.1 up to 10% by weight of a bleach stable perfume whichcomprises 50-100% by weight of the bleach stable schiff base having thestructure: ##STR73## having a Lipoxidase-inhibiting capacity of at least50% or a Raoult variance ratio of at least 1.1 as defined according toU.S. Pat. No. 4,663,068 incorporated by reference herein, with theschiff base being stable in the presence of sodium perboratetetrahydrate or any other alkali metal perborate tetrahydrate andN,N,N',N'-tetraacetyl ethylenediamine (TEAD) according to the bleachstability test as defined in said U.S. Pat. No. 4,663,068 incorporatedby reference herein, the bleach stable deodorant schiff base having aMalodor Reduction Value of from 0.25 up to 3.0 as measured by theMalodor Reduction Value test defined in said U.S. Pat. No. No. 4,663,068incorporated by reference herein.

The peroxy bleach activator may be exemplified by the following peroxybleach activators:

N,N,N',N'-tetracetyl ethylenediamine;

N,N,N',N'-tetracetyl glycoluril;

Glucose pentaacetate;

Sodium acetoxybenzene sulphonate;

Sodium nonanoyloxybenzene sulphonate;

Sodium octanoyloxybenzene sulphonate; and

mixtures thereof.

The non-soap anionic detergent active compound may be selected from thegroup consisting of sodium and potassium alkyl sulphates, sodiumpotassium and ammonium alkyl benzene sulphonates, sodium alkyl glycerylether sulphates, sodium coconut oil fatty acids monoglyceride sulphatesand sulphonates, sodium and potassium salts of sulphuric acid esters ofhigher (C₉ -C₁₈) fatty alcohol-alkylene oxide, the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide, sodium and potassium salts of fatty acid amides of methyltaurine, alkane monosulphonates, olefin sulphonates and mixturesthereof.

The nonionic detergent active compound may be selected from the groupconsisting of reaction products of alkylene oxides with alkyl (C₆ -C₂₂)phenols, the condensation products of aliphatic (C₈ -C₁₈) primary orsecondary linear or branched alcohols with ethylene oxide, products madeby condensation of ethylene oxide with the reaction products ofpropylene oxide and ethylene diamine, long-chain tertiary amine oxides,long-chain phosphine oxides and dialkyl sulphoxides and mixturesthereof.

What is claimed is:
 1. A schiff base reaction product produced accordingto the process of reacting methyl anthranilate having the structure:##STR74## with ethyl vanillin having the structure: ##STR75##
 2. Aschiff base reaction product having the structure: ##STR76##